Photovoltaic thin-film cell produced from metallic blend using high-temperature printing

ABSTRACT

The metallic components of a IB-IIIA-VIA photovoltaic cell active layer may be directly coated onto a substrate by using relatively low melting point (e.g., less than about 500° C.) metals such as indium and gallium. Specifically, CI(G)S thin-film solar cells may be fabricated by blending molten group IIIA metals with solid nanoparticles of group IB and (optionally) group IIIA metals. The molten mixture may be coated onto a substrate in the molten state, e.g., using coating techniques such as hot-dipping, hot microgravure and/or air-knife coating. After coating, the substrate may be cooled and the film annealed, e.g., in a sulfur-containing or selenium-containing atmosphere.

CROSS-REFERENCE TO RELATED APPLICATION

This application is continuation of U.S. patent application Ser. No. 10/836,307 filed Apr. 30, 2004, which is a continuation-in-part of and claims priority to commonly-assigned, co-pending application Ser. No. 10/782,017 entitled SOLUTION-BASED FABRICATION OF PHOTOVOLTAIC CELL, filed Feb. 19 2004, the entire disclosures of which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention is related to photovoltaic cells and more particularly to fabrication of IB-IIIA-VIA active layers for such cells.

BACKGROUND OF THE INVENTION

Low-cost production of solar cells on flexible substrates using printing or web coating technologies is promising highly cost-efficient alternative to traditional silicon-based solar cells. Recently, solar cells fabricated from alloys of copper (Cu) and indium (In) with selenium (Se) or sulfur (S) have been developed. Such solar cells (known as CIGS cells) have been produced using a variety of approaches, including sputtering, evaporation, and chemical vapor deposition. However, vacuum-based deposition systems such as sputtering and evaporation can only control the stoichiometric ratio of co-deposited materials with high-cost, low-speed processes. This limitation severely impacts production of solar cells where active layer composition must be tightly controlled. For example, the synthesis of a high-performance CIGS active layer is only possible within a narrow ratio of copper to indium and/or gallium. Co-evaporation or co-sputtering of the individual CIGS elements requires controlled coordination of the deposition rates in a manner that is uniform both spatially across a substrate and from run to run. It is difficult to deposit uniform films on large areas using coincident vapor phase processes. Furthermore, deposition processes such as sputtering and evaporation typically result in less efficient materials utilization, as deposited material is also transported from the source target to chamber walls or shields rather than just the substrate.

Thus, there is a need in the art for an alternative route in the fabrication of CIGS active layers that overcomes the above disadvantages.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the present invention can be readily understood by considering the following detailed description in conjunction with the accompanying drawings, in which:

FIG. 1 is a schematic diagram illustrating fabrication of photovoltaic cells according to an embodiment of the present invention.

FIG. 2 is a schematic diagram of a photovoltaic cell according to an embodiment of the present invention.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

Although the following detailed description contains many specific details for the purposes of illustration, anyone of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope of the invention. Accordingly, the exemplary embodiments of the invention described below are set forth without any loss of generality to, and without imposing limitations upon, the claimed invention.

According to embodiments of the present invention, the metallic components of a IB-IIIA-VIA photovoltaic cell active layer may be directly coated onto a substrate by using relatively low melting point (e.g., less than about 500° C.) metals such as indium and gallium. Specifically, CI(G)S thin-film solar cells may be efficiently and reproducibly fabricated directly from a metallic solution by blending one or more molten group IIIA metals with solid nanoparticles containing group IB and (optionally) group IIIA metals. The molten mixture may be coated onto a thin film substrate in the molten state, e.g., using coating techniques such as hot-dipping, hot microgravure and/or air-knife coating. After coating, the substrate may be cooled and annealed in a sulfur-containing or selenium-containing atmosphere.

It should also be understood that group IB, IIIA, and VIA elements other than Cu, In, Ga, Se, and S may be included in the description of the IB-IIIA-VIA alloys described herein, and that the use of a hyphen (“—”e.g., in Cu—Se or Cu—In—Se) does not indicate a compound, but rather indicates a coexisting mixture of the elements joined by the hyphen. Where several elements can be combined with or substituted for each other, such as In and Ga, or Se, and S, in embodiments of the present invention, it is not uncommon in this art to include in a set of parentheses those elements that can be combined or interchanged, such as (In, Ga) or (Se, S). The descriptions in this specification sometimes use this convenience. Finally, also for convenience, the elements are discussed with their commonly accepted chemical symbols.

Group IB elements suitable for use in the method of this invention include copper (Cu), silver (Ag), and gold (Au). Preferably the group IB element is copper (Cu). Group IIIA elements suitable for use in the method of this invention include gallium (Ga), indium (In), aluminum (Al), and thallium (Tl). Preferably the group IIIA element is gallium (Ga) or indium (In). Group VIA elements of interest include selenium (Se), sulfur (S), and tellurium (Te), and preferably the group VIA element is either Se or S.

FIG. 1 depicts an apparatus 101 that may be used in conjunction with embodiments of the present invention. In the apparatus 101, a coating unit 106, applies a film 114 of a molten mixture 110 to a substrate 104. The molten mixture 110 includes a molten group IIIA element containing nanoparticles of a group IB element and (optionally) another group IIIA element. The substrate 104 may be a metal foil, e.g., aluminum, molybdenum or stainless steel foil, a molybdenum-coated aluminum or stainless steel foil, a molybdenum-coated plastic foil, or another thin flexible sheet material that can withstand processing at the temperature of the molten mixture. By way of example nanoparticles containing copper and gallium may be mixed with molten indium to form the molten mixture 110. By way of example, the molten mixture 110 may be made starting with a molten mixture of Indium and/or Gallium (commercially available, e.g., from Alfa Aesar of Ward Hill, Mass.). Copper nanoparticles may then be added to the molten mixture. Copper nanoparticles are available commercially, e.g., from Materials Modification Inc., of Fairfax, Va., or such nanoparticles can be produced using any of a variety of well-developed techniques, including but not limited to (i) the electro-explosion of copper wire, (ii) mechanical grinding of copper particles for a sufficient time so as to produce nanoparticles, or (iii) solution-based synthesis of copper nanoparticles from organometallic precursors. Alternatively, the temperature of a Cu—Ga—In mixture may be adjusted (e.g. cooled) until a solid forms. The solid may be ground at that temperature until small nanoparticles (e.g., less than 5 nm) are present. Selenium and/or sulfur may optionally be added to the molten mixture 110, and/or the coating 114 before, during or after coating the substrate 104.

By way of example the coating unit 6 may be a hot microgravure coater having a vat 108 of the molten mixture 110 and a microgravure roller 112. The vat 108 may be heated by a heater (not shown) to keep the mixture in the molten state. For example, indium has a melting point of about 156° C. The heater preferably keeps the molten mixture 110 at or above this temperature. The roller 112 contacts both the molten mixture 110 and a surface of the substrate 104. The roller 112 may include indentations that collect measured portions of the molten mixture from the vat 108 as the roller 112 rotates. The roller 112 rotates such that, at the point of contact with the substrate 104, the substrate and roller surfaces are moving in opposite directions relative to each other.

In alternative embodiments of the invention the coating unit 106 may be a hot-dip deposition unit that immerses the substrate in a bath of molten metal or alloy for a specific time. Hot-dip deposition is suitable if melting temperature of the molten mixture 110 is less than that of the substrate 104, the coating 114 is not too brittle and the substrate 104 has a suitable shape (e.g., no small openings.) Such coating techniques, which are commonly used to apply coatings of tin (melting point 230° C.) and zinc (melting point 419° C.), may be readily adapted to coatings based on molten indium (melting point 156° C.). An additional advantage is that such techniques can apply coatings at very high speeds (e.g., 2000 feet per minute). Coatings as thin as 1-2 microns may be obtained with hot dip coating.

In other alternative embodiments, the coating unit 106 may include an extrusion coater or hot melt coater to cast the molten mixture. Extrusion dies in an extrusion coater can form a free film that rapidly cools to form the coating 114 as a thin solid film that can subsequently be laminated to the substrate 104. An advantage of the free film approach is that the coating 114 may be processed to reduce its thickness and improve uniformity before it is laminated to the substrate 104. Alternatively, the substrate 104 may be backed by a cooled roll so that the coating 114 rapidly solidifies on the substrate 104.

In yet another alternative embodiment, the coating unit 106 may be a plasma spray coater. The plasma spray process involves the spraying of molten or heat softened material onto a surface to provide a coating. Material in the form of powder is injected into a very high temperature plasma flame, where it is rapidly heated and accelerated to high velocity. The hot material impacts the substrate surface and rapidly cools forming a coating. This plasma spray process carried out correctly is called a “cold process” as the substrate temperature can be kept low during processing avoiding damage, metallurgical changes and distortion to the substrate material.

The apparatus 101 may include a doctor blade 116 to doctor the coating 114 to a desired thickness, e.g., between 1-10 microns, preferably between about 1 micron and about 4 microns thick. The doctor blade 116 may be a solid blade or an air knife having a gas manifold with a plurality of nozzles that direct a high velocity stream of air or other gas at the coating 114 on the substrate 104. Such an air knife may doctor the coating 114 to the desired thickness with a sharp air jet.

Some high-volume batch processes for coating the substrate with the molten mixture, e.g., hot-dipping, could potentially coat both sides of a substrate at one time. However, it may be desirable to primarily coat only one side, since double-sided coating can result in waste of valuable components of the molten mixture, e.g., indium. To avoid such waste, two substrates may be temporarily attached together “back-to-back” to form a dual substrate having, in effect, two front sides. The dual substrate may then be wound into a coil and coated such that both front surfaces get coated while the back surfaces do not. Preferably, the substrates are attached in a manner that allows them to be separated from each other after processing. By way of example the substrates may be attached with a low-strength adhesive or electrostatic film applied to the back side of one or both substrates. Alternatively, an edge where the two substrates join may be sealed, e.g., with a tape, so that the molten mixture cannot reach the back sides during processing. Processing the substrate in this fashion wastes less of the molten mixture and may increase the area of the substrate that can be coated at one time.

Additional processing of the coating 114 may take place before or after the coating cools to solidify. Such additional processing may include exposure to a vapor containing one or more elements of group VIA to complete the IB-IIIA-VIA coating. For example, the coating 114 may be exposed to selenium vapor to selenize a Cu—In—Ga coating to form a Cu—In—Ga—Se alloy. The alloy may have the general formula CuIn_(1-x)Ga_(x)(S, Se)₂, where x is between 0 and 1. By way of example the stoichiometric ratio of copper to indium may be about 0.9. Alternatively, the coating 114 may be exposed to a vapor containing hydrogen selenide (H₂Se) or hydrogen sulfide (H₂S)

As set forth above, the molten mixture includes a low-melting point metal of group IB (e.g., indium and/or gallium) and particles containing elements of group IIIA and/or IB, e.g., copper and gallium. The particles may be between about 1 nanometer and about 1 micron in size, more preferably between 1 nm and 100 nm, and most preferably between 1 nm and 40 nm. The decreased particle size can significantly lower both the melting point and the sintering temperature required, especially below 10-20 nm (see e.g., C R M Wronski, “The Size Dependence of the Melting point of Small Particles of Tin” in the British Journal of Applied Physics vol. 18, No. 12, (December 1967) pp 1731-1737, IOP Publishing, Bristol, UK; L. H. Allen, “Nanocalorimetry Studies of Materials: Melting Point Depression and Magic Nanostructures” NNUN Abstracts 2002/Materials, Physics, Processes & Characterization, pp 40; Zhang et al., 2000. “Size-dependent melting point depression of nanostructures: Nanocalorimetric measurements.” Phys. Rev. B 62 (15): 548-557; Lisecki et al. 2000. “Annealing Process of Anisotropic Copper Nanocrystals.” 2. Rods. Langmuir 16: 8807-8808).

Generally, reduction in the melting point is inversely proportional to the particle radius, i.e., the smaller the nanoparticles, the lower the melting point. Smaller particles also tend to pack closer together and make better contact with each other. Reduction in size from bulk material to particles in about the 10-40 nm regime can already show significant differences in melting point and other altered physical and chemical properties. With much smaller particle sizes, e.g. in the nanometer size range, the surface area of particles will increase and nanoparticles will be in intimate contact with each other. In addition, in the nanometer size range, the reactivity of the particles and interaction between nanoparticles will be enhanced. This may help particles fuse together much easier thus enhancing the cohesion of the resulting CIGS layer (W. H. Qi, et al. in “China—EU Forum on Nanosized Technology” Beijing, P. R. China. Dec. 2002. pp 86-92). This promotes coalescence between neighboring particles during sintering.

The sizes of the nanoparticles may be distributed over a relatively narrow range, e.g. with the majority of particles of a given type being within about 40% of an average particle size for that type. Note that for a molten mixture containing particles of different chemical types, e.g., different elemental metals, or different binary combinations, the different types of particles may have different average sizes so that the particles all melt at about the same temperature. By appropriately adjusting the particle size distribution amongst the particles of different materials in the mixture, it is possible for all the particles to melt at about the same temperature during sintering and yield more uniform crystalline phases. This enhances the electronic properties of the crystals in the resulting CIGS film. By contrast, in the prior art, CuInSe₂ powders generated, e.g., by a milling or nebulizing process to create powder precursors have typically contained a mixture of both small and large particles, resulting in a relatively broad size distribution. The presence of such a broad size distribution results in poor film formation. In particular, smaller particles tend to melt first while big particles remain unmelted. Further, particles of different sizes can non-uniformly distribute within a film. This heterogeneity leads to defects in film growth, decreases the uniformity and size of crystal grains, and negatively impacts the electronic properties (e.g., resistivity, bandgap, and carrier transport) of the CIGS layer upon incorporation into a photovoltaic device such as a solar cell.

Therefore, according to embodiments of the present invention, the nanoparticles (e.g., elemental metal nanoparticles, quantum nanoparticles, or metallic nanoparticles) in the molten mixture may be about 1-nm to about 100-nm in diameter. The nanoparticles may have a substantially uniform size distribution, characterized by an average nanoparticle size D. For example, the nanoparticles may have sizes within about 40% of D. If the average particle size is less than about 5 nm, then the variation can be bigger, e.g., between about 1 nm and about 2 nm. In this case, the resulting range of melting points is still sufficiently small to be considered to have a narrow particle size distribution. By way of example, the particles in the liquid may include Cu with In or Ga and Se or S in a stoichiometric ratio of approximately CuIn_(1-x)Ga_(x)(S, Se)₂, where x is between 0 and 1.

Methods to make nanoparticles of the desired materials having the desired narrow particle size distribution include controlling the reaction conditions under which the nanoparticles are made or using size-selective precipitation and/or other techniques such as ultrafiltration. Nanoparticles in different categories may be incorporated into the molten mixture 110. These categories include but are not limited to: (1) Ternary nanoparticles such as CuInSe₂ or CuInGa nanoparticles; (2) Binary nanoparticles such as CuSe and In₂Se₃ nanoparticles; (3) Elemental metallic nanoparticles such as Cu and In nanoparticles; (4) Metal halides dissolved in chelating agents; and (4) Metal salts. Other techniques for forming nanoparticles include includes laser ablation, mechanical milling, grinding, nucleation from vapor, exploding wires by electrical current surge, thermal treatment, sonolysis, pulse radiolysis, electrochemical reduction or chemical reduction.

Nanoparticles may or may not melt during deposition of the molten mixture 110 to form the film 114. Subsequent annealing steps (either before and optionally after selenization) can improve the microstructure of the grains in the film 114 through recrystallization and other heat-driven processes. As a result, copper atoms can be effectively and widely dispersed in the annealed film even in the absence of prior Cu nanoparticle melting.

Therefore, in a preferred embodiment of the invention, Cu nanoparticles may be added to the molten In (and optionally molten Ga) but without melting the nanoparticles. Instead the nanoparticles may be distributed throughout the molten material during the initial deposition of the film 114. Then, during a later annealing step, the film can be heated to a temperature sufficient to cause Cu atoms to diffuse and be more widely distributed through the material of the film 114.

By way of example, after deposition, the film 114 (e.g., a CIGS film) may be annealed for up to 30 minutes at a temperature of about 150-300° C. After annealing, the film may optionally be exposed to selenium vapor at about 300-500° C. for about 30-45 minutes to ensure the proper stoichiometry of Se in the film. Both of these steps may improve the microstructure and increase the grain size of the resulting CIGS layer.

Photovoltaic Devices

A IB-IIIA-VIA alloy layer fabricated as described above can be used in the active layer of photovoltaic cell, e.g., of the type shown in FIG. 2. The solar cell 200 generally includes a substrate or base layer 202, a base electrode 204, a IB-IIIA-VIA layer 206, a window layer 208, and a transparent electrode 210. The base layer 202 may be made from a thin flexible material suitable for roll-to-roll processing. By way of example, the base layer may be made of a metal foil, such as titanium, a polymer such as polyimide or a metallized plastic. The base electrode 204 is made of an electrically conducive material. By way of example, the base electrode 204 may be a layer of stainless steel or molybdenum, e.g., about 0.5 microns to about 1 micron thick.

By way of example, and without limitation, the IB-IIIA-VIA layer 206 may include material of the general formula CuIn_(1-x)Ga_(x)(S or Se)₂. The IB-IIIA-VIA layer 206 may be fabricated by depositing a film of a molten mixture, e.g., roughly 1 to 10 microns thick on the base electrode 204. The film may be cooled to solidify the IB-IIIA-VIA layer 206. The IB-IIIA-VIA layer 206 may be about 1 micron to about 4 microns thick after cooling. By using a molten mixture of the type described above, the IB-IIIA-VIA layer 206 may be formed at a temperature compatible with the underlying substrate 202 and electrode 204. An optional adhesion layer 203 may facilitate bonding of the electrode 204 to the substrate 202.

After annealing, the film may optionally be exposed to selenium vapor at about 300-500° C. for about 30-45 minutes to ensure the proper stoichiometry of Se in the film. To carry out such a Se vapor exposure, the film, if deposited on a flexible substrate, can be wound into a coil and the coil can be coated so that the entire roll is exposed at the same time, substantially increasing the scaleability of the Se vapor exposure process through such a high-volume batch process, e.g., as described above.

The window layer 208 is typically used as an interface between the bandgaps of the different materials making up the IB-IIIA-VIA layer 206. By way of example, the window layer may include cadmium sulfide (CdS), zinc sulfide (ZnS), or zinc selenide (ZnSe) or some combination of two or more of these. Layers of these materials may be deposited, e.g., by chemical bath deposition, typically to a thickness of about 50 nm to about 100 nm.

The transparent electrode 210 may include a transparent conductive oxide layer 209, e.g., zinc oxide (ZnO) or aluminum doped zinc oxide (ZnO:Al), which can be deposited using any of a variety of means including but not limited to sputtering, evaporation, CBD, electroplating, CVD, PVD, ALD, and the like. If the substrate is flexible and the deposition technique is ALD or CBD or the like, a coiled/wound flexible substrate can be exposed so that the entire roll is processed at one time, e.g., as described above. The transparent electrode 210 may further include a layer of metal (e.g., Ni, Al or Ag) fingers 211 to reduce the overall sheet resistance.

An optional encapsulant layer (not shown) provides environmental resistance, e.g., protection against exposure to water or air. The encapsulant may also absorb UV-light to protect the underlying layers. Examples of suitable encapsulant materials include one or more layers of polymers, such as tetrafluoroethylene-hexafluoropropylene-vinylidenflouride-copolymer (THV), polyethylene terephthalate (PET), ethylene vinyl acetate (EVA), and/or Mylar®. Mylar is a registered trademark of E. I. du Pont de Nemours and Company of Wilmington, Del. Inorganic materials, such as glass and plastic foils, metalized plastic foils, and metal foils may also be used for the encapsulant layer. The encapsulant layer may also include nitrides, oxides, oxynitrides or other inorganic materials. Alternatively, the encapsulants may include Tefzel® (DuPont), tefdel, thermoplastics, polyimides, polyamides, nanolaminate composites of plastics and glasses (e.g. barrier films), and combinations of the above. For example, a thin layer of (relatively expensive) EVA/polyimide can be laminated to thick layer of (much less expensive) PET.

Embodiments of the present invention provide for low-cost, high-volume production of large area photovoltaic devices. Further, in contrast to prior solution-based approaches that have focused on lower temperature CIGS processing, embodiments of the present invention utilize higher-temperature CIGS processing, e.g., in a temperature range of about 150-250° C., with hot-melt coating equipment, and enable direct deposition of a thin film from a molten metallic paste.

Furthermore, embodiments of the present invention are compatible with roll-to-roll manufacturing of photovoltaic cells and modules that can be readily scaled up to high production volumes.

While the above is a complete description of the preferred embodiment of the present invention, it is possible to use various alternatives, modifications and equivalents. Therefore, the scope of the present invention should be determined not with reference to the above description but should, instead, be determined with reference to the appended claims, along with their full scope of equivalents. In the claims that follow, the indefinite article “A”, or “An” refers to a quantity of one or more of the item following the article, except where expressly stated otherwise. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase “means for.” 

1. A method for forming an active layer coating, the method comprising the steps of: forming a molten mixture of one or more metals of group IIIA and metallic nanoparticles containing elements of group IB; and coating a substrate with a film formed from the molten mixture.
 2. A photovoltaic cell, comprising: a base electrode; a top electrode; and an active layer disposed between the base electrode and top electrode, the active layer containing a IB-IIIA-VIA alloy, wherein the active layer is formed from a molten mixture containing one or more metals of group IIIA and metallic nanoparticles containing elements of group IB.
 3. The cell of claim 2 wherein at least one of the base electrode and top electrode is transparent.
 4. The cell of claim 2 further comprising a layer of cadmium sulfide (CdS), zinc sulfide (ZnS), or zinc selenide (ZnS) or some combination of two or more of these disposed between the active layer and the top electrode. 